JP3433457B2 - Flame retardant adhesive and heat shrinkable tube - Google Patents
Flame retardant adhesive and heat shrinkable tubeInfo
- Publication number
- JP3433457B2 JP3433457B2 JP21733692A JP21733692A JP3433457B2 JP 3433457 B2 JP3433457 B2 JP 3433457B2 JP 21733692 A JP21733692 A JP 21733692A JP 21733692 A JP21733692 A JP 21733692A JP 3433457 B2 JP3433457 B2 JP 3433457B2
- Authority
- JP
- Japan
- Prior art keywords
- flame
- adhesive
- retardant
- flame retardant
- shrinkable tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S428/00—Stock material or miscellaneous articles
- Y10S428/92—Fire or heat protection feature
- Y10S428/921—Fire or flameproofing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
- Y10T428/1328—Shrinkable or shrunk [e.g., due to heat, solvent, volatile agent, restraint removal, etc.]
- Y10T428/1331—Single layer [continuous layer]
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Insulating Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【発明の詳細な説明】
【０００１】
【産業上の利用分野】本発明は熱収縮チューブの内面に
塗布される難燃性のホットメルト接着剤及びそれを内面
に塗布した熱収縮性チューブに関するものである。
【０００２】
【従来の技術】従来、熱収縮チューブの内面に塗布され
るホットメルト接着剤の樹脂組成物としては、ＥＶＡ、
ＥＥＡ、変性ポリオレフィン、ポリアミド、フッ素樹脂
等が使用されている。又これに粘着性を付与するためク
マロン・ インデン樹脂、フェノール・ テルペン系樹脂、
ポリブテン樹脂等が粘着付与剤として添加されている。
一方、難燃剤としては、臭素系、塩素系が実用化されて
いるが、難燃効果の大きい臭素系難燃剤がよく使用され
る。これらのものは、ヘキサブロモベンゼン、デカブロ
モジフェニルオキシド、エチレンビス・ テトラブロモフ
タルイシド、テトラブロモ・ ビスフェノールＡ誘導体、
オクタブロモジフェニルオキシド等が挙げられる。又無
機難燃剤としては、三酸化アンチモン、五酸化アンチモ
ン、水酸化マグネシウム、ポリリン酸アンモニウム等が
挙げられる。
【０００３】又高分子材料中に微粉末が分散されている
場合、チクソトロピー（揺変性）を示すことがよく知ら
れており、この性質はシーリング材料、ペイント等に広
く応用されている。チクソトロピーを発現させるために
添加される微粉末としては、例えば特公昭54-37663号公
報、特公昭55-29107号公報等に示されるように、平均粒
子径数μｍのシリカや 1.2μｍ以下の水和アルミナ等が
知られている。又難燃性と防水性を要求される分野では
上記物質と難燃剤又は難燃性を有する物質との組合せも
検討されており、例えば特開昭 61-254686号公報が知ら
れている。
【０００４】
【発明が解決しようとする課題】難燃化された内層用ホ
ットメルト接着剤は、その目的上、加熱により流動性を
増す性質のものであるから、燃焼時にその流動性が増加
し、たれ流れて延焼の原因となる。一方チクソトロピー
を利用した難燃性接着剤は、比較的外力が加わらない状
態である燃焼時に粘度が見かけ上増加し、たれ流れ等の
不都合を防止することもできるが、チクソトロピー効果
を強く出せるよう、微粉末の添加量を増加すると、高流
動性が要求される防水加工時にも接着剤の粘度が高くな
りすぎて、十分な充填ができず、防水性が十分発揮でき
ないという問題点がある。
【０００５】
【課題を解決するための手段】本発明は上述の問題点を
解消し、外力が加わった時良好な流れ性を示し、火災時
たれ落ちのない難燃性接着剤をチューブ内面に塗布した
ワイヤーハーネスの防水に適用される熱収縮性チューブ
を提供するもので、その特徴は、ＭＩ（１９０℃）値が
３０〜２２０である樹脂組成物１００重量部に対し、臭
素系又は塩素系難燃剤を５〜４０重量部、無機難燃剤を
１〜３０重量部、平均粒子径が０．０１μｍ〜４０μｍ
の範囲にある微粉末を０．１〜２０重量部添加した難燃
性接着剤を塗布した熱収縮性チューブにある。
【０００６】本発明において用いられる樹脂組成物とし
ては、エチレンと酢酸ビニルを主なモノマーとして重合
されたもので、融点が60〜 100℃の範囲にあるもの、融
点が80〜 190℃の範囲にあるポリエステル樹脂、あるい
は融点が50〜90℃の範囲にあるポリアミド樹脂等が挙げ
られる。微粉末としては0.01〜40μｍの範囲にあるシリ
カが用いられる。又塩素系難燃剤としては塩素含有量が
60重量％以上のもの、臭素系難燃剤としては臭素含有量
が80重量％以上のものが用いられる。
【０００７】さらに、本発明の難燃性接着剤を内面に塗
布するチューブ材料としては、ポリエチレン、エチレン
−酢酸ビニル共重合体、エチレン−アクリル酸エチル共
重合体のいずれか１つ又は２つの混合物からなるベース
樹脂に、塩素系難燃剤又は臭素系難燃剤を５〜40重量
部、無機難燃剤を１〜30重量部、酸化防止剤、加工助剤
等を添加したものが用いられる。
【０００８】
【作用】本発明において難燃剤として樹脂組成物 100重
量部に対して臭素系難燃剤を５〜40重量部、無機難燃剤
を１〜30重量部を添加する。この場合、できるだけ少な
い添加量で難燃性を付与できるようにするためには、臭
素系難燃剤の場合分子中に占める臭素の割合が80重量％
以上、塩素系難燃剤の場合塩素の割合が65重量％以上が
好ましく、無機難燃剤としてはアンチモン酸化物、特に
三酸化アンチモンが好ましく、ホットメルト接着剤の難
燃性は十分高められる。例えばＭＩのもっと低い樹脂、
例えばポリエチレンをベースとする組成物に添加した場
合、ＵＬ−94のＶ−１以上、樹脂を選択すればＶ−０レ
ベルの難燃性も達成できる。
【０００９】しかし、ホットメルト接着剤の場合、加熱
によりチューブと被覆物の間に十分に流れ込み、隙間な
く充填される必要がある。このためには、高温時に粘度
が十分に低いことが必要である。しかし、この高温時に
粘度が低いことは、燃焼時にたれ流れが起こり、火のつ
いたままの接着剤が床面等へ落下して延焼の原因とな
る。従ってチューブ被覆加工時に十分に流れ、燃焼時に
たれ流れのない相反する性質が求められる。
【００１０】この相反する性質を接着剤に付与するため
にはチクソトロピーと呼ばれる現象を利用すればよい。
これは外力がかかっている状態では流動性が高く、外力
を取り去ると流動性が極端に低下する現象である。この
性質を樹脂に与えるには、粒径の細かい粉体、例えば平
均粒子径が0.01μｍ〜40μｍの範囲にある微粉体を添加
するとよい。
【００１１】しかし、チクソトロピー効果を強く実現さ
せると、高い流動性が求められる通常の収縮加工時に、
接着剤の流動性を低下させることになり、高い防水性を
求められる用途には、その難燃性も合せ高いバランスが
要求される。これまで公知となっているものは、どれも
難燃性及び防水性とチクソトロピー効果のバランスが不
充分であり、ワイヤーハーネスの防水には適用できなか
った。さらにワイヤーハーネスを構成する電線の絶縁層
の材質は、一般にＰＶＣ、ポリエチレン、エチレン−酢
酸ビニル共重合体を主な材料とする１種又は２種以上の
混合物からなっており、これらに対して、冷熱サイクル
及び応力のかかった状態で適切な防水性を維持するため
には、図２に示すような測定方法で、ポリエチレン、Ｐ
ＶＣ、エチレン−酢酸ビニル共重合体に対し、 0.2kg／
cm以上の接着力が必要であることから種々の実験から見
出した。なお、図２において、10は難燃性接着剤、11は
難燃性接着剤の補強シート、12は接着試験用被着体、13
は固定側チャック、14は上昇側チャックである。以上よ
り添加される微粉末の粒径は0.01μｍ〜40μｍの範囲で
あることが必要であり、特に0.01μｍ〜４μｍの範囲が
好ましい。この粉末の材質は特に限定しないが、接着
性、熱老化性に与える影響を考慮し、物理的に不活性と
考えられるシリカ（SiO2）が好ましい。
【００１２】なお、難燃性接着剤及びチューブへは使用
される温度環境に応じて、適切な量、種類の酸化防止剤
（例えばチバガイギー社製イルガノックス1010、住友化
学製スミライザーＢＨＴ等が挙げられる）を添加しても
よい。
【００１３】
【実施例】表１及び表２に試料例、後述する試験の結果
を示す。表１中の試料例1〜10及び表２中の試料例15〜1
6は実施例、表２中の試料例11〜14及び17は比較例であ
る。
【００１４】
【表１】
【００１５】
【表２】【００１６】各樹脂組成物及び添加剤は、ロール温度 1
40℃に加熱したロール上で15分間混練した後、プレスに
てシートを作成した。そしてＵＬ94に規定する燃焼試験
条件で厚み２mm、長さ 127mm、幅12.7mmに打ち抜いたも
のを用いて難燃性評価を行った。
Ｖ−０：２回接炎後、毎回10秒以上の有炎の燃焼をし
ないこと。
有炎又は無炎の燃焼が支持クランプまで達しないこ
と。
有炎の滴下物により下にしいた脱脂綿を着火させない
こと。
２回目接炎後、30秒以上の無炎の燃焼をしないこと。
Ｖ−１：２回接炎後、毎回30秒以上炎を出して燃焼し
ないこと。
有炎又は無炎の燃焼が支持クランプまで達しないこ
と。
有炎の滴下物により下にしいた脱脂綿を着火しないこ
と。
２回目接炎後、60秒以上の無炎の燃焼をしないこと。
Ｖ−２：２回接炎後、毎回30秒以上炎を出して燃焼し
ないこと。
有炎又は無炎の燃焼が支持クランプまで達しないこ
と。
有炎の滴下物により下にしいた脱脂綿を着火すること
がある。
２回目接炎後、60秒以上の無炎の燃焼をしないこと。
【００１７】又本発明の難燃性接着剤の評価には、ポリ
エチレン、ＰＣＶ、ＥＶＡの各樹脂からなる平坦で表面
が平滑なシートを作成し、この上に接着剤シート（幅２
cm、厚さ２mm）をのせ、さらにフッ素樹脂コーティング
を施した鉄板で挾み、 150℃×10分間加圧下で加熱し、
この後、室温まで冷却して各シートと接着剤シート間の
接着力を、インストロン社製引張り試験機にて引張り速
度50mm／min で引張り測定した。測定値はシート幅２cm
であることから２cmで除し、単位kg／cmとして示した。
【００１８】
【試作例】本発明の難燃性接着剤を内面に塗布した熱収
縮性チューブを用いて、図１に示すようにＰＶＣ絶縁電
線からなるハーネス接続部に被覆し、加熱収縮させた。
１及び２はＰＶＣ絶縁電線、1a及び2aは上記電線の導
体、３は導体接続部、４は加熱収縮せしめたチューブで
ある。
【００１９】このようなハーネス接続部を水平に保持し
て、炎を15秒間当てた後、30秒以内に自然消火でき、残
り４回、同様に繰返してもすべて30秒以内に自然消火で
き、さらに、いずれの回でも、有炎、無炎を問わず落下
物を生じないという卓越した難燃性を有することが確認
できた。これと同時に、図３に示すように塩水中に24時
間浸漬した後、そのまま50V ＤＣ印加して漏れ電流を測
定しても、 0.5μＡ以下という高い防水性を示した。さ
らに、接着剤に酸化防止剤を１〜５重量部添加した場合
には 125℃×40日放置後でも、上記の防水性を保持でき
た。
【００２０】
【発明の効果】以上説明したように、本発明の難燃性接
着剤によれば、外力が加わった時に良好な流れ性を示
し、かつ火災時には延焼の原因となるたれ流れがないた
め、熱収縮チューブの内層剤として用いると特に有効で
ある。従って、このような熱収縮チューブは、高度な難
燃性及び防水性が求められる用途、例えば自動車用ハー
ネス等に利用するとき、極めて効果的である。Description: BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant hot-melt adhesive applied to the inner surface of a heat-shrinkable tube and to a heat-shrinkable tube coated with the same. It is. [0002] Conventionally, as a resin composition of a hot melt adhesive applied to the inner surface of a heat shrinkable tube, EVA,
EEA, modified polyolefin, polyamide, fluororesin and the like are used. Also, to impart tackiness to this, coumarone / indene resin, phenol / terpene resin,
Polybutene resin and the like are added as a tackifier.
On the other hand, bromine-based and chlorine-based flame retardants have been put to practical use, but bromine-based flame retardants having a large flame-retardant effect are often used. These include hexabromobenzene, decabromodiphenyl oxide, ethylenebistetrabromophthaluiside, tetrabromobisphenol A derivatives,
Octabromodiphenyl oxide and the like can be mentioned. Examples of the inorganic flame retardant include antimony trioxide, antimony pentoxide, magnesium hydroxide, ammonium polyphosphate and the like. It is well known that when a fine powder is dispersed in a polymer material, it exhibits thixotropy (thixotropic), and this property is widely applied to sealing materials, paints and the like. Examples of the fine powder added to express thixotropy include silica having an average particle size of several μm and water having a particle size of 1.2 μm or less as disclosed in, for example, Japanese Patent Publication No. 54-37663 and Japanese Patent Publication No. 55-29107. Japanese alumina and the like are known. In addition, in the field where flame retardancy and waterproofness are required, combinations of the above substances with a flame retardant or a substance having flame retardancy have been studied. For example, Japanese Patent Application Laid-Open No. 61-254686 is known. [0004] Since the hot-melt adhesive for the inner layer which has been made flame-retardant has a property of increasing its fluidity by heating for the purpose, its fluidity increases during combustion. , Which may cause dripping and spread of fire. On the other hand, the flame-retardant adhesive using thixotropic, the viscosity is apparently increased at the time of burning in a state where relatively no external force is applied, it is possible to prevent inconveniences such as dripping, but as a strong thixotropic effect, When the amount of the fine powder added is increased, the viscosity of the adhesive becomes too high even in the waterproofing process where high fluidity is required, so that there is a problem that sufficient filling cannot be performed and the waterproofness cannot be sufficiently exhibited. SUMMARY OF THE INVENTION The present invention solves the above-mentioned problems, and provides a flame-retardant adhesive which exhibits good flowability when an external force is applied and which does not drip in a fire. The present invention provides a heat-shrinkable tube used for waterproofing of a coated wire harness, and is characterized by a bromine-based or chlorine-based with respect to 100 parts by weight of a resin composition having an MI (190 ° C) value of 30 to 220. 5 to 40 parts by weight of a flame retardant, 1 to 30 parts by weight of an inorganic flame retardant, and an average particle diameter of 0.01 μm to 40 μm
In a heat-shrinkable tube coated with a flame-retardant adhesive containing 0.1 to 20 parts by weight of a fine powder in the range of (1) to (4). The resin composition used in the present invention is obtained by polymerizing ethylene and vinyl acetate as main monomers and having a melting point in the range of 60 to 100 ° C. and a melting point in the range of 80 to 190 ° C. Examples include a certain polyester resin, or a polyamide resin having a melting point in the range of 50 to 90 ° C. Silica in the range of 0.01 to 40 μm is used as the fine powder. The chlorine content of chlorine-based flame retardants
The brominated flame retardant having a bromine content of 80% by weight or more is used as the brominated flame retardant. Further, as a tube material for applying the flame-retardant adhesive of the present invention to the inner surface, any one or a mixture of two of polyethylene, ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer is used. A resin obtained by adding 5 to 40 parts by weight of a chlorine-based or bromine-based flame retardant, 1 to 30 parts by weight of an inorganic flame retardant, an antioxidant, a processing aid, or the like to a base resin made of According to the present invention, 5 to 40 parts by weight of a brominated flame retardant and 1 to 30 parts by weight of an inorganic flame retardant are added to 100 parts by weight of a resin composition as a flame retardant. In this case, in order that the flame retardancy can be imparted with the smallest possible addition amount, the bromine-based flame retardant should have a bromine content of 80% by weight in the molecule.
As described above, in the case of a chlorine-based flame retardant, the chlorine content is preferably 65% by weight or more. As the inorganic flame retardant, antimony oxide, particularly antimony trioxide is preferred, and the flame retardancy of the hot melt adhesive is sufficiently enhanced. For example, a resin with lower MI,
For example, when added to a composition based on polyethylene, flame retardancy of V-0 level or higher can be achieved by selecting a resin, V-1 of UL-94 or higher. However, in the case of the hot melt adhesive, it is necessary to sufficiently flow between the tube and the coating by heating and to be filled without gaps. For this purpose, it is necessary that the viscosity be sufficiently low at high temperatures. However, the low viscosity at the high temperature causes a dripping flow at the time of combustion, causing the ignited adhesive to drop to the floor or the like, causing fire to spread. Therefore, it is required to have a contradictory property in which a sufficient flow occurs during the tube coating process and there is no dripping flow during the combustion. In order to impart this contradictory property to the adhesive, a phenomenon called thixotropy may be used.
This is a phenomenon in which the fluidity is high when an external force is applied, and the fluidity extremely decreases when the external force is removed. In order to impart this property to the resin, a powder having a fine particle size, for example, a fine powder having an average particle size in the range of 0.01 μm to 40 μm may be added. However, when the thixotropic effect is strongly realized, during normal shrinkage processing, which requires high fluidity,
In applications where the flowability of the adhesive is reduced and high waterproofness is required, a high balance is required in addition to its flame retardancy. All of the known materials have a poor balance between flame retardancy and waterproofness and the thixotropic effect, and cannot be applied to waterproof wire harnesses. Further, the material of the insulating layer of the electric wire constituting the wire harness is generally made of one or a mixture of two or more kinds mainly composed of PVC, polyethylene, and ethylene-vinyl acetate copolymer. In order to maintain proper waterproofness under a thermal cycle and under stress, polyethylene, P
0.2kg / VC, ethylene-vinyl acetate copolymer
It was found from various experiments because an adhesive force of at least cm was required. In FIG. 2, 10 is a flame-retardant adhesive, 11 is a reinforcing sheet of a flame-retardant adhesive, 12 is an adherend for an adhesion test, 13
Denotes a fixed-side chuck, and 14 denotes an ascending-side chuck. From the above, the particle size of the fine powder to be added needs to be in the range of 0.01 μm to 40 μm, and particularly preferably in the range of 0.01 μm to 4 μm. Although the material of the powder is not particularly limited, silica (SiO 2 ), which is considered to be physically inert, is preferable in consideration of the influence on the adhesiveness and the heat aging property. The flame-retardant adhesive and the tube may have an appropriate amount and type of antioxidant (for example, Irganox 1010 manufactured by Ciba-Geigy Co., Sumilizer BHT manufactured by Sumitomo Chemical Co., Ltd.) according to the temperature environment used. ) May be added. EXAMPLES Tables 1 and 2 show sample examples, and the results of tests described later.
Is shown. Sample Examples 1 to 10 in Table 1 and Sample Examples 15 to 1 in Table 2
6 is an example, and sample examples 11 to 14 and 17 in Table 2 are comparative examples.
You. [Table 1] [Table 2] Each of the resin composition and the additives are used at a roll temperature of 1
After kneading for 15 minutes on a roll heated to 40 ° C., a sheet was formed by pressing. Flame retardancy evaluation was performed using a punched piece having a thickness of 2 mm, a length of 127 mm, and a width of 12.7 mm under the combustion test conditions specified in UL94. V-0: Do not burn for 10 seconds or more each time after flame contact twice. Flammable or flameless combustion should not reach the support clamp. Do not ignite absorbent cotton placed below with flaming drops. After the second flame contact, do not burn without flame for more than 30 seconds. V-1: After burning twice, do not burn by emitting flame for more than 30 seconds each time. Flammable or flameless combustion should not reach the support clamp. Do not ignite the absorbent cotton placed below with flaming drops. After the second flame contact, do not burn without flame for more than 60 seconds. V-2: After burning twice, do not burn by emitting flame for 30 seconds or more each time. Flammable or flameless combustion should not reach the support clamp. Flammable drops may ignite absorbent cotton underneath. After the second flame contact, do not burn without flame for more than 60 seconds. In order to evaluate the flame-retardant adhesive of the present invention, a flat and smooth surface sheet made of polyethylene, PCV and EVA resins was prepared, and an adhesive sheet (width 2) was formed on the sheet.
cm, thickness 2 mm), sandwich it with an iron plate coated with fluororesin, and heat it under pressure at 150 ° C for 10 minutes.
Thereafter, the sheet was cooled to room temperature, and the adhesive strength between each sheet and the adhesive sheet was measured by a tensile tester manufactured by Instron at a tensile speed of 50 mm / min. Measured value is 2cm sheet width
Therefore, it was divided by 2 cm, and was shown as a unit kg / cm. Using a heat-shrinkable tube coated with the flame-retardant adhesive of the present invention on the inner surface, a harness connection portion made of a PVC insulated wire was coated as shown in FIG. 1 and heat-shrinked. .
1 and 2 are PVC insulated wires, 1a and 2a are conductors of the wires, 3 is a conductor connecting portion, and 4 is a tube that has been heated and shrunk. After holding such a harness connection portion horizontally and applying a flame for 15 seconds, the fire can be spontaneously extinguished within 30 seconds, and the remaining four times can be spontaneously extinguished within 30 seconds even if repeated. Further, it was confirmed that the composition had excellent flame retardancy, in which no falling objects were generated regardless of the presence or absence of flame in any of the times. At the same time, as shown in FIG. 3, even after immersion in salt water for 24 hours, 50 V DC was directly applied and the leakage current was measured, showing a high waterproofness of 0.5 μA or less. Further, when 1 to 5 parts by weight of an antioxidant was added to the adhesive, the above waterproof property could be maintained even after standing at 125 ° C. for 40 days. As described above, according to the flame-retardant adhesive of the present invention, good flowability is exhibited when an external force is applied, and there is no dripping which causes fire spread in a fire. Therefore, it is particularly effective when used as an inner layer agent of a heat-shrinkable tube. Therefore, such a heat-shrinkable tube is extremely effective when used for applications requiring high flame retardancy and waterproofness, for example, harnesses for automobiles.
【図面の簡単な説明】
【図１】本発明の難燃性接着剤を内面に塗布した熱収縮
性チューブをワイヤーハーネスの接続部に被覆した例の
説明図である。
【図２】接着力測定方法の説明図である。
【図３】防水性評価装置の説明図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an explanatory diagram of an example in which a heat-shrinkable tube in which a flame-retardant adhesive of the present invention is applied to an inner surface is coated on a connection portion of a wire harness. FIG. 2 is an explanatory diagram of a method for measuring an adhesive force. FIG. 3 is an explanatory diagram of a waterproof evaluation device.
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) C09J 9/00 C09J 11/04 C09J 11/06 H01B 17/58 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 7 , DB name) C09J 9/00 C09J 11/04 C09J 11/06 H01B 17/58
Claims (1)
縮性チューブであって、チューブ内面にＭＩ（１９０
℃）値が３０〜２２０である樹脂組成物１００重量部に
対し、臭素系又は塩素系難燃剤を５〜４０重量部、無機
難燃剤を１〜３０重量部、平均粒子径が０．０１μｍ〜
４０μｍの範囲にある微粉末を０．１〜２０重量部添加
した難燃性接着剤を塗布したことを特徴とする熱収縮性
チューブ。(1) A heat-shrinkable tube used for waterproofing a wire harness, wherein MI (190) is provided on the inner surface of the tube.
C) value of 100 to 100 parts by weight of a resin composition having a value of 30 to 220, 5 to 40 parts by weight of a bromine-based or chlorine-based flame retardant, 1 to 30 parts by weight of an inorganic flame retardant, and an average particle diameter of 0.01 µm to
A heat-shrinkable tube coated with a flame-retardant adhesive to which 0.1 to 20 parts by weight of a fine powder in a range of 40 µm is added.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21733692A JP3433457B2 (en) | 1991-07-26 | 1992-07-22 | Flame retardant adhesive and heat shrinkable tube |
| US08/037,380 US5346539A (en) | 1991-07-26 | 1993-03-26 | Flame-retardant adhesive |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20993591 | 1991-07-26 | ||
| JP3-209935 | 1991-07-26 | ||
| JP21733692A JP3433457B2 (en) | 1991-07-26 | 1992-07-22 | Flame retardant adhesive and heat shrinkable tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05214305A JPH05214305A (en) | 1993-08-24 |
| JP3433457B2 true JP3433457B2 (en) | 2003-08-04 |
Family
ID=26517762
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21733692A Expired - Fee Related JP3433457B2 (en) | 1991-07-26 | 1992-07-22 | Flame retardant adhesive and heat shrinkable tube |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US5346539A (en) |
| JP (1) | JP3433457B2 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9523002D0 (en) * | 1995-11-09 | 1996-01-10 | Raychem Ltd | Flame-retarded adhesive composition |
| US20100219369A1 (en) * | 2005-12-20 | 2010-09-02 | Industrial Technology Research Institute | Composition of thermal interface material |
| GB0718320D0 (en) * | 2007-09-20 | 2007-10-31 | Tyco Electronics Ltd Uk | Product and method for wire seal |
| JP2009099332A (en) * | 2007-10-16 | 2009-05-07 | Meidensha Corp | Insulated voltage device |
| JP5679696B2 (en) * | 2009-05-22 | 2015-03-04 | 日東電工株式会社 | UV-curable adhesive composition, adhesive layer, adhesive sheet and method for producing the same |
| JP5711713B2 (en) * | 2012-10-01 | 2015-05-07 | 住友電気工業株式会社 | Multi-layer heat recovery article |
| JP5651161B2 (en) * | 2012-12-20 | 2015-01-07 | 住友電気工業株式会社 | Multi-layer heat recovery article, wire splice and wire harness |
| JP6002027B2 (en) * | 2012-12-20 | 2016-10-05 | 住友電気工業株式会社 | Multi-layer heat recovery article, wire splice and wire harness |
| US10553386B2 (en) | 2013-11-15 | 2020-02-04 | Eaton Intelligent Power Limited | High voltage, reinforced in-line fuse assembly, systems, and methods of manufacture |
| JP6420581B2 (en) * | 2014-07-15 | 2018-11-07 | 住友電気工業株式会社 | High fluidity polyamide resin |
| DE102015112529B4 (en) * | 2015-07-30 | 2021-12-09 | Lisa Dräxlmaier GmbH | Procedure for leak testing a cable consisting of at least two lines |
| CA3081227A1 (en) | 2019-05-22 | 2020-11-22 | Nvent Services Gmbh | Flame-resistant heat shrink assemblies for trace heating cables |
| KR102138928B1 (en) * | 2020-05-22 | 2020-07-29 | 주식회사 코리아오션텍 | Wire connector with fire fighting function |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL293800A (en) * | 1962-06-08 | |||
| US3418267A (en) * | 1965-09-01 | 1968-12-24 | Du Pont | Flame-resistant polyamides and process thereof |
| BE794470A (en) * | 1972-01-27 | 1973-07-24 | Bayer Ag | SELF-EXTINGUISHING POLYAMIDIC MOLDING COMPOSITIONS |
| GB8321643D0 (en) * | 1983-08-11 | 1983-09-14 | Ici Plc | Fire retardant polyamide compositions |
| DE3424147A1 (en) * | 1984-06-30 | 1986-01-09 | Bayer Ag, 5090 Leverkusen | METAL OXIDE ON ORGANIC HALOGEN-BASED CARRIER AS A FLAME RETARDANT |
-
1992
- 1992-07-22 JP JP21733692A patent/JP3433457B2/en not_active Expired - Fee Related
-
1993
- 1993-03-26 US US08/037,380 patent/US5346539A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| US5346539A (en) | 1994-09-13 |
| JPH05214305A (en) | 1993-08-24 |
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